Mechanism of catalysis of the thio-Claisen rearrangement

Journal Article · Tue Apr 07 23:00:00 EST 1981 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00397a028· OSTI ID:6206165

Kwart, H; Miles, W H; Horgan, A G; Kwart, L D

The cyclization-induced rearrangement mechanism proposed by Overman to account for nucleophilic catalysis of the thio-Claisen rearrangement has been tested by application of two criteria, viz., the secondary kinetic deuterium isotope effect at the ..beta.. (side chain) carbon in phenyl allyl sulfide and the substituent rate effect. The results (k/sub H/k/sub D/ = 1.05 and log k/sub xp/k/sub H/ = 0.25 sigma/sup +/) do not support the mechanism. Instead, they can be construed to support the previously validated mechanism of nucleophilic triggering of sigmatropic rearrangement.

• Research Organization: Univ. of Delaware, Newark
• OSTI ID: 6206165
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 103:7; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
400302 -- Organic Chemistry-- Isotope Effects-- (-1987)
ALKENES
CHEMICAL REACTIONS
CLAISEN CONDENSATION
DATA
DEUTERIUM
EXPERIMENTAL DATA
HYDROCARBONS
HYDROGEN ISOTOPES
INFORMATION
ISOTOPE EFFECTS
ISOTOPES
LIGHT NUCLEI
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
STABLE ISOTOPES